IVAS 2022 banner
IVES 9 IVES Conference Series 9 IVAS 9 IVAS 2022 9 Hemisynthesis, NMR Characterization and UHPLC-Q-Orbitrap /MS² identification of (+)-Catechin oxidation products in red wines and grape seed extracts

Hemisynthesis, NMR Characterization and UHPLC-Q-Orbitrap /MS² identification of (+)-Catechin oxidation products in red wines and grape seed extracts

Abstract

(+)-Catechin—laccase oxidation dimeric standards were hemi-synthesized using laccase from Trametes versicolor in a water-ethanol solution at pH 3.6. Eight fractions corresponding to eight potential oxidation dimeric products were detected. The fractions profiles were compared with profiles obtained with two other oxidoreductases: polyphenoloxidase extracted from grapes and laccase from Botrytis cinerea. The profiles were very similar, although some minor differences suggested possible dissimilarities in the reactivity of these enzymes. Five fractions were then isolated and analyzed by 1D and 2D NMR spectroscopy. The addition of traces of cadmium nitrate in the samples solubilized in acetone-d6 led to fully resolved NMR signals of phenolic protons, allowing the unambiguous structural determination of six reaction products, one of the fractions containing two enantiomers. These products were then analyzed in grape seed extracts and red wines (UHPLC-Q-Orbitrap MS). The different dimers had different fragmentation patterns according to their interflavan linkage position. Oxidation dimeric compounds had a specific fragment ion at m/z 393, missing for B-Type dimers fragmentations. A fragment ion at m/z 291 occurred and was specific for oxidation dimeric compounds with a C-O-C linkage. Higher level oxidation products had abundant specific fragments: m/z 425, 397 and 245. These fragmentations were useful to identify them in complex samples such as grape seed extracts and wines. Three grape varieties and three ripening stages were selected and the corresponding seed extracts were obtained. The analyses revealed an increasing trend for the oxidation markers during grape ripening. The analysis of Syrah wines (2018, 2014, 2010) showed a decreasing trend of these molecules during wine ageing which might be due to further oxidation.

DOI:

Publication date: June 23, 2022

Issue: IVAS 2022

Type: Article

Authors

Saucier Cedric1, Deshaies Stacy1, Le Guernevé Christine1,2, Sommerer Nicolas1,2, Garcia Lucas Suc François1, Mouls Laetitia1

1SPO, Université de Montpellier, INRAE, Institut Agro, UMR SPO, Faculté de Pharmacie, 15 avenue Charles Flahault, 34000 Montpellier, France
2INRAE, PROBE Research Infrastructure, PFP Polyphenol Facility, 34060 Montpellier, France

Contact the author

Keywords

wine, grape, polyphenol,oxidation, catechin

Tags

IVAS 2022 | IVES Conference Series

Citation

Related articles…

Pruned vine biomass exclusion from a clay loam vineyard soil – examining the impact on physical/chemical properties

The wine industry worldwide faces increasing challenges to achieve sustainable levels of carbon emission mitigation. This project seeks to establish the feasibility of harvesting winter pruned vineyard biomass (PVB) for potential use in carbon footprint reduction, through its use as a renewable biofuel for energy production. In order to make this recommendation, technical issues such as the potential environmental impact, chemical composition and fuel suitability, and logistical challenges of harvesting biomass needs to be understood to compare with the results from similar studies. Of particular interest is the role PVB plays as a carbon source in vineyard soils and what effect annual removal might have on soil carbon sequestration. A preliminary trial was established in the Waite Campus vineyard (University of Adelaide) to test current management strategies. Vines are grown in a Eutrophic, Red Dermosol clay loam soil with well managed midrow swards. A comparison was undertaken of mid-row treatments in two 0.25 Ha blocks (Shiraz and Semillon), including annual cultivation for seed bed preparation, the deliberate exclusion of PVB (25 years) and incorporation of PVB (13 years) at an average of 3.4 and 5.5 Mg/Ha-1 for Shiraz and Semillon respectively. In both 0-10cm and 10-30cm soil core sample depths, combined soil carbon % measures in the desired range of 1.80 to 3.50, were not significantly different between treatments or cultivars and yielded an estimated 42 Mg/ha-1 of sequestered soil carbon. Other key physical and chemical measures were likewise not significantly different between treatments. Preliminary results suggest that in a temperate zone vineyard, managed such as the one used in this study, there is no long term negative impact on soil carbon sequestration through removing PVB. This implies that growers could confidently harvest PVB for use in several end fates including as a bio fuel.

Downscaling of remote sensing time series: thermal zone classification approach in Gironde region

In viticulture, the challenges of local climate modelling are multiple: taking into account the local environment, fine temporal and spatial scales, reliable time series of climate data, ease of implementation and reproducibility of the method. At the local scale, recent studies have demonstrated the contribution of spatialization methods for ground-based climate observation data considering topographic factors such as altitude, slope, aspect, and geographic coordinates (Le Roux et al, 2017; De Rességuier et al, 2020). However, these studies have shown questions in terms of the reproducibility and sustainability of this type of climate study. In this context, we evaluated the potential of MODIS thermal satellite images validated with ground-based climate data (Morin et al, 2020). Previous studies have been encouraging, but questions remain to be explored at the regional scale, particularly in the dynamics of the massive use of bioclimatic indices to classify the climate of wine regions. The results at the local scale were encouraging, but this approach was tested in the current study at the regional scale. Several objectives were set: 1) to evaluate the downscaling method for land surface temperature time series, 2) to identify regional thermal structure variations. We used weekly minimum and maximum surface temperature time series acquired by MODIS satellites at a spatial resolution of 1000 m and downscaled at 500 m using topographical variables. Two types of analyses were performed:

Variety and climatic effects on quality scores in the Western US winegrowing regions

Wine quality is strongly linked to climate. Quality scores are often driven by climate variation across different winegrowing regions and years, but also influenced by other aspects of terroir, including variety. While recent work has looked at the relationship between quality scores and climate across many European regions, less work has examined New World winegrowing regions. Here we used scores from three major rating systems (Wine Advocate, Wine Enthusiast and Wine Spectator) combined with daily climate and phenology data to understand what drives variation across wine quality scores in major regions of the Western US, including regions in California, Oregon and Washington. We examined effects of variety, region, and in what phenological period climate was most predictive of quality. As in other studies, we found climate, based mainly on growing degree day (GDD) models, was generally associated with quality—with higher GDD associated with higher scores—but variety and region also had strong effects. Effects of region were generally stronger than variety. Certain varieties received the highest scores in only some areas, while other varieties (e.g., Merlot) generally scored lower across regions. Across phenological stages, GDD during budbreak was often most strongly associated with quality. Our results support other studies that warmer periods generally drive high quality wines, but highlight how much region and variety drive variation in scores outside of climate.

Phenolic composition of Tempranillo Blanco grapes changes after foliar application of urea

Our research aimed to determine the effect and efficiency of foliar application of urea on the phenolic composition of Tempranillo Blanco grapes. The field experiment was carried out in 2019 and 2020 seasons and the plot was located in D.O.Ca Rioja (North of Spain). The vineyard was Vitis vinifera L. Tempranillo Blanco and grafted on Richter-110 rootstock. The treatments were control (C), whose plants were sprayed with water and three doses of urea: plants were sprayed with urea 3 kg N/ha (U3), 6 kg N/ha (U6) and 9 kg N/ha (U9). The applications were performed in two phenological stages, pre-veraison (Pre) and veraison (Ver). Also, each of the treatments was repeated one week later. Control and treatments were performed in triplicate and arranged in a randomised block design. Grapes were harvested at optimum ripening stage. High-performance liquid chromatography was used to analyse the phenolic composition of the grapes. Finally, the results obtained from the analytical determinations – flavonols, flavanols and non-flavonoid (hydroxybenzoic acids, hydroxycinnamic acids and stilbenes) – were studied statistically by analysis of variance. The results showed that, in 2019, U6-Pre and U9-Pre treatments increased the hydroxybenzoic acid content in grapes, and also all foliar treatments applied at Pre enhanced the stilbene concentration. Moreover, U3-Ver was the only treatment that rose flavonol and stilbene contents in the Tempranillo Blanco grapes. In 2020, all treatments applied at Pre enhanced the flavonol concentration in grapes. Furthermore, U3-Pre and U9-Pre treatments increased stilbene content in grapes. Nevertheless, the hydroxybenzoic acid content was improved by U6-Ver and U9-Ver and besides, hydroxycinnamic acid concentration in grapes was increased by all treatments applied at Ver. In conclusion, the lower and highest dose of urea (U3 and U9), applied at pre-veraison, were the best treatments to improve the Tempranillo Blanco grape phenolic composition.

20-Year-Old data set: scion x rootstock x climate, relationships. Effects on phenology and sugar dynamics

Global warming is one of the biggest environmental, social, and economic threats. In the Douro Valley, change to the climate are expected in the coming years, namely an increase in average temperature and a decrease in annual precipitation. Since vine cultivation is extremely vulnerable and influenced by the climate, these changes are likely to have negative effects on the production and quality of wine.
Adaptation is a major challenge facing the viticulture sector where the choice of plant material plays an important role, particularly the rootstock as it is a driver for adaptation with a wide range of effects, the most important being phylloxera, nematode and salt, tolerance to drought and a complex set of interactions in the grafted plant.
In an experimental vineyard, established in the Douro Region in 1997, with four randomized blocs, with five varieties, Touriga Nacional, Tinta Barroca, Touriga Franca and Tinta Roriz, grafted in four rootstocks, Rupestris du Lot, R110, 196-17C, R99 and 1103P, data was collected consecutively over 20 years (2001-2020). Phenological observations were made two to three times a week, following established criteria, to determine the average dates of budbreak, flowering and veraison. During maturation, weekly berry samples were taken to study the dynamics of sugar accumulation, amongst other parameters. Climate data was collected from a weather station located near the vineyard parcel, with data classified through several climatic indices.
The results achieved show a very low coefficient of variations in the average date of the phenophases and an important contribution from the rootstock in the dynamic of the phenology, allowing a delay in the cycle of up to10-12 days for the different combinations. The Principal Component Analysis performed, evaluating trends in the physical-chemical parameters, highlighted the effect of the climate and rootstock on fruit quality by grape varieties.